Process for the preparation of elastic products and substitutes for natural lacs.



1 Finally GEORGES NUTH, MARSEILLE, FRANCE.-

PROCESS FOR: THE PREPARATION OF ELASTIC PRODUCTS AND SUBSTITUTES FOR NATURAL LACS.

No Drawing.

To all whom it may concern:

Be it known that I, GEORGES NU'IH, a citizen of the Republic" of France, residing at Marseille, Bouches du Rhone, France, have invented a Process for the Preparation of Elastic Products and Substitutes for Natural Lacs, of which the following is a specification.

In the specification of my copending application Serial No'. 522,773 are described processes for the preparation of, elastic products and substitutes for natural lacs by the action of amins upon factices or, in other words, upon the products of the reac tion of certain fatty bodies with the protohalogen compounds of'sulfur. As the result of his researches on this subject the applicant has found that the condensation products of these same fatty bodies with other halogen derivatives of sulfur likewise lend themselves to reaction with the amins, even ammonia, giving 'riseto new interesting products and particularly to elastic substances and substitutes for natural lacs. This other group of condensation products formed between fatty bodies and halogen derivatives of sulfur will likewise be designated factices. Furthermore the said researches have proved that it is-not only the primary and secondary amins which react with the factices, but the tertiary amins do so also, giving rise to the formation of elastic products varying from soft to hard.

The nature of the action of the amins upon the factices depends upon the nature of the amin and the working conditions. Thus for example the amin may cause the formation of halogenated hydrogen, which may result from the substitution of one or more atoms of halogen-in the factice by the amin radicals, or from the separation from.

the molecules of the factice of one ,or more molecules of halogenated hydrogen, .which may thus cause new unsaturated linkings. the two reactions may take place simultaneously. The action of the amins upon the factices described in the specification of my copending application Serial No. 522,773 may also be explained on similar lines. Besides the protohalogen compounds of sulfur which form the subject matter \of the prior patent hereinabove referred to, the applicant has chiefly in view, among the Specification of Letters latent. I

Application filed December 27, 1911. Serial No. $68,148.

' various authors.

other halogen derivatives of sulfur, the dichlorid of sulfur of commerce. The existence of dichlorid of sulfur as a distinct really exist and form the major portion of the dichlorid of sulfur of commerce.

The products obtained by the action of famins' upon the products of. condensation between this other group of halogen derivatives of sulfur and certain fatty bodies, are viscous masses up to the solid state, and elastie, and often possess great cohesion, or are hard and brittle masses. In consequence of the creation of the new unsaturated linkings above mentioned, these masses can ordinarily be vulcanized by means of sulfur, or halogen compounds of sulfur. Thus for example elastic products which vary from soft to hard and which resemble intheir properties vulcanized or raw rubber can be so obtained. On the other hand these same derivatives from factices and amins, if they are not already very hard,,have a tendency to undergo further solidification under certain conditions. This phenomenon is probably due to polymerization. It is produced by the action of time, heat, oxidizing agents,

and also by auto-oxidation. When so transformed these products form materials which are either elastic or brittle and which ordinarily, lend themselves to vulcanization, yielding elastic or brittle products. In like manner products slightly vulcanized can be further hardened by polymerization.

The products in question are generally insoluble inal'cohol of ninety (90) degrees, but mostly so when they are freshly prepared. They are soluble in benzol provided that complex amins have not been used in their preparation. This solubility is greatly diminished by polymerization or vulcanization in accordance with the degree of polymerization or vulcanization. p The materials of which the general properties have just been described may be employed, if elastic, for numerous purposes as substitutes for rubber and gutta-percha.

Patented Nov. 2, 1915.

On the other hand however, these materials,

' resistance to heat, water, and alkalis they are distinguished with advantage fromthe varnishes obtained by means of natural lacs or gums. As hereinbefore stated the bodies to be considered for the preparation of these products are the fatty bodies such for example as linseed, China wood, poppy, maize,

cotton, sesame, colza, almond, earth nut,

olive, castor and codliver oils, neats foot oil and palm oil: finally the fatty oxidized, polymerized, sulfureted, sulfureted and oxidized, oxidized and sulfureted or nitrated oils, in general the fatty oils and bodies which are capable of reacting with the halogen derivatives of sulfur.

lVith regard to'the amins, those of both the fatty and aromatic series may be employed, even ammonia and substances which easily give up or evolve ammonia or amins, such for example as anilin, para-toluidin, metaxylidin, alpha naphthylamin, parachloranilin, meta-nitranilin, 1:5. dehydrothiotoluidin, phenylhydrazin, meta-amidophenol, amidonaphthol 1 :5, metaamido-benzoic acid, sulfanilic acid, naphthionic acid, amido-naphthosulfonic acid G or the salts of these acids: mono-methylanilin, diphenylamin, para-tolyl-alpha-naphthyl-amin, dimethylanilin, acetanilid, phenetedin, benzamid, meta-phenylenediamin', benzidin, mono methyl paraphenylene-diamin, di methyl para phenylene diamin, para amidodiphenylamin, acetylbenzidin, diamidodiphenylurea, amidoazobenzol, paraamidoazobensol alpha naphthylanrin, triamidoazobenzol, rosanilin, indulins, safiranins, pyridin, etc.; finally, ammonia, trimethylamin, benzylamin: amidoacetic, phenylamidoacetic and amido-succinic acids or their salts: the ethyl ester of amidoacetic acid, carbamid, thioearbamid, guanidin, ethylenediamin, sodamid, anilid of potassium, cyanamid, et'c.

For the preparation of these substances in question the amin is caused to act directly on the factice, (after-this latter has been purified if this is an advantage) or the reactive substances may be diluted with products suitable for this operation. The work maybe carried out in open or closed vessels according to requirements. The addition of certain products, such as acetate of soda, carbonate of lime, chlorid' of copper, etc., which facilitate the reaction between halogen products and amins, is sometimes allowable or desirable. The polymerization of these masses may be produced in suitable ways as for example: by the action of air, by spreading out the mass in thin layers.

By heating the mass on the water bath or in gen through the hot solution, or a current of ozone through the cold solution of the dinitroanilin I greases mass. By mixing the products or their so-v V lutilons withkoxidizing bodies either hot or col The vulcanization with sulfur, may be ef fected according to the processes in use for the vulcanization of rubber, but vulcaniza tion may also be carried out insolution.

vulcanization with halogen compounds. of sulfur is preferably effected with a suitable solution of the mass. By way of example there will now be given, first 'of all, the methods of preparation of some factices by means of oils and dichlorid of sulfur of commerce. It is obvious of course that by varying the proportions between the oils and the dichloride of sulfur difi'erent factices will beobtained.

Example A: A mixture of ten (10) parts of linseed oil and forty (40) parts of toluene is mixed, while being well stirred, with a solution of three (3) parts of dichlorid of sulfur in fifteen (15) parts of toluene. A gelatinous, transparent and nearly colorless massgradually forms which separates from the toluene. The mass becomes elastic and has the appearance of the ordinary linseed yellow color is formed. This is left to stand for some time and then spread out to eliminate the toluene. A clotted product results which is of a very slight yellow color, elastic to compression, but possessing very little cohesion.

Example C: Fifteen (15) parts of poppy oil mixed with forty five (45) parts of toluene are mixed with a solution of four a) parts of dichlorid of sulfur in twelve (12) parts of toluene. Within twentyfour hours v,

the mixture will have been transformed into a colorless mass which is gelatinous and slightly viscous. When freed from the toluene it forms a colorless, soft,-rather sticky product, elastic to compression and possessin%slight cohesion.

xample D: By causing twentyfive (25) parts of castor oil diluted with seventy five (75) parts of toluene to react with a solution of six (6) parts of dichlorid of sulfur in fifteen (15) parts of toluene a compact mass is formed which is cut up to better separate the solvent from it and a dry product which is almost colorless and rather elastic to compression is finally formed.

Example E: A mixture of five (5) parts of oliveoil and five (5) parts of benzol is added to one (1) part of dichlorid of sulfur previously diluted with one (1) part of-benwhen freed from the toluene, becomes a faintly colored, clotted product, elastic to compression but possessing scarcely any coheslon.

Example G: Three (3) parts of dichlorid of sulfur previously diluted with fifteen (15) parts of benzol are caused to act on a mixture of fifteen (15) parts of oxidized linseed oil and forty (40) arts of benzol. A solid, transparent, brown-yellow colored mass is rapidly formed, which, after evaporation of the benzol, becomes a brown mass elastic to compression. The oxidized linseed oil is prepared by causing a current of air to pass through the linseed oil heated to about two hundred and fifty (250) degrees 0., until the oil has become viscous.

Example H: Fifteen (15) parts of sulfureted castor oil are mixed with thirty (30) parts of benzol, and a mixture of two (2) parts of dichlorid of sulfur and ten (10) parts of benzol are then added. The mixture is afterward gently heated. The mass thickens by degreesand after having been allowed to .stand the .benzol is evaporated off and a brown product thus obtained which is slightly sticky, rather elastic to compression and possesses a slight amount of cohesion. For the preparation of the sulfureted castor oil, the castor oil is heated to about one hundredand eighty (180) degrees C. and there is then introduced, little by little, keeping the temperature of the oil at from one hundred and eighty to two hundred (180 to 200) degrees (1., a quantity of sulfur corresponding to four per cent. of the quantity of castor oil employed.

of sulfureted boiled linseed oil and fourteen (14) parts of heavy benzin is added to one 1) part of dichlorid of sulfur. Little by little this mixture solidifies and forms a gelatinous and glutinous mass. Washed with alcohol and dried, this substance becomes firmer .but still remains rather glutinous. The sulfureted boiled linseed oil is prepared by heating the boiled linseed oil of commerce to from one hundred and sixty to one hundred and seventy (160' to 170) de-v grees C. and then introducing into it little by little a quantity of sulfur corresponding to four per cent. of the weight of the boiled linseed oil. Afterward the temperature is kept up for about an hour at from one hundred and seventy to one hundred and eighty (170 to 180) degrees C By way of example and .without the invention being limited thereto, of the new substances in question will be hereinafter given. In. this specification the lengths of time and temperatures must always be understood to be approximate. The temperatures given are those in general which are obtained by means of an oil bath.

Example 1: In a vessel on an oil bath are placed three (3) parts of anilin and one 1) part of linseed oil factice by dichlorid of sulfur, obtained as in Example A The mixture is heated to about one hundred and twenty-five (125) degrees, C. and this temsundry methods of formationv with stirring. The factice disappears little by little. The clear) liquid is poured into about ten (10) parts of toluene and then left to stand so-that the anilin hydrochlorid which is formed may settle. The mixture is then filtered. The filtrate is then mixed with alcohol which precipitates the new product in the form of a very fine and faintly colored precipitate which coagulates rapidly. After some time, the supernatant liquid is decanted. The residue forms a liquid'mass. By being washed with alcohol it solidifies and finally becomes a slightly gelatinous product which is elastic and of a slight brown color. The decanted liquid is worked up by known processes for the purpose of recovering the anilin, the toluene and the alcohol. The new product prepared as has just been described, is fairly well soluble in benzol yielding a limpid and almost colorless solution, which gives no precipitate with oil of turpentine, ether or ni- I which the solubility is very much lessened. Example I: A mixture of seven (7) parts It is obvious of course that the new product might be effectively separated and isolated in other ways, as for example by pouring the product of the fusion of the anilin factice in a thin stream into water and causing at the same time a jet of dilute hydrochloric acid to flow in so as to transform the excess of anilin into its salt. The reaction product will separate in the form of a viscous mass which will be washed with water, then dissolved in benzol or dried, according to the use to whichit is intended that it shall be put. The anilin may also be removed by subjecting the fused anilin factice to a current of steam.

Example 2: A hot solution of ten (10) parts of para-chloranilin in fifty five (55) 'in the filtrate a brown fine parts of sulfur dichlorid linseed oilfactice and then heated for about ten."

(Example'A) I hours at one hundred and thirty five (135). degrees C.

and stringy mass.- Washed with alcohol, it

becomes transformed into an elastic mass 7 which is slightly gelatinous, Its solution in toluene leaves when exposed to the, aira nearly colorless, adherent and easily handled firm and exhibits a good degree of elasticity.

film. 1 1 p 4' Example 3: Amixture of seven (7) parts of metanitranilin, forty-five (45)- .parts ofheavy benzin and ten (10) parts of sulfur. dichlorid linseed oil factice (Example A) is heated for six to seven hours at'from one hundred and thirty to one hundred and forty (130 to 1 10) degrees() The fused mass is then diluted with fifty (50) parts of tolueneand separated from the meta-nitranilin hydrochlorid by filtration. Alcohol produces precipitate which coagulates-shortly afterward. The supernatant liquid is removed by decantation. Washed with alcohol the residue forms a slightly soft mass of a dark brown color whichis very elastic to compression and when pulled. Its solution in toluene which is greenish-yellow, leaves when exposed to air, a greenish-yellow, adherent, transparent film which hardens well.

Example 4: One (1) part of sulfur dichlorid China wood oil factice (see Example B) is caused to react with one (1) part of para-toluidin and five (5) parts ofheavy benzin, the mixture being heated to one hundred and twenty five (125) degrees C. and then at from one hundred and twenty five to one hundred and thirty (125 to 130) degrees C. for from seven to eight hours. The cooled fused mass is diluted with about double its volume of toluene and is then filtered. After precipitation of the filtrate with alcohol, the supernatantli uid is decanted off, the residue washed with alcohol andthere is thus obtained a soft masswhich is slightly gelatadherent film w dred and thirty five (135) degrees C. and

The liquid formed is then dis-1 p solved in benzol, and filtered to recover 'theq lalcoliol; "After some time,

para-chloranilin hydrochlorid. By ,the ad-r dition of alcohol tothe filtrate the new prqdgg uct separates and coagulates, pretty rapidly... Shortly afterward the supernatant'liquid is,

decanted. The residueforms arather solid; dred (100) degrees C. this product four (1) parts of monoethyl menace then for from tento twelve hours at from one hundred and thirty five to one hundred;

and forty tio'n' lis thus'obt ained which is diluted with toluene, filtered and then precipitated with the precipitate settles andwhen collected and washed with alcohol, it forms .a very viscous, stringy, elastic product which is soluble in benzol. Heated for aboutthree .hours'at one hun- 1S transformed .into a black .brownmass, which is ratholijsoftand rather elastic., Mixed with ten per. ,cent. of .sulfur and vulcanized for one, hour at one'hundred and thirty five (135) degrees (1., this mass becomes very fQtd'ldO) degrees C. A solu- Example 6:. One (1) part of sulfur dichlorid China wood oil factice (Example This mixture is heated to about one hundred and thirty (130) degrees C. and then for twelve hours at from one hundred and thirty to one hundred and thirty five (130 to 135) degrees C. After dilution of the fused mass with toluene it alcohol, the filtrate deposits a brown liquid precipitate which when collected and washed with alcohol, becomes rather solid, viscous, elastic and soluble in benzol. Heated on a water bath for two hours this product becomes firmer Example 7 A mixture of one (1) part of sulfur dichlorid China wood oil factice (Example B), one (1) part of rosanilin and five (5) parts of Water are heated in an autoclave for from twenty five to thirty hours at about one hundred and twenty (120) degrees C. .The mass obtained is first washed with boiling water, then extracted with hot alcohol to eliminate therosanilin. When so .purified and then dried, the mass is a clotted product of a dark violet color possessing a slight degree of elasticity to compression. It is insoluble in water, oil of turpentine and benzol, but very slightly soluble in alcohol, yielding a violet solution.

Example 8 A mixture of two (2) parts of sulfur dichlorid poppy oil factice (Example C), three (3) parts of alpha-naphthyl-amin and six (6) parts of heavy benzine is heated forfrom five to six hours at from one hundred and thirty five to one hundred and forty five (135 to 145) degrees O. The cooled fused mass is diluted with toluene and the alpha-nap'hthylamin hydrochlorid formed then filtered off. By precipitation of the filtrate with alcohol, a liquid mass separates which, when collected and washed with alcohol, becomes viscous and stringy. Its solution in toluene may be used as a varnish. Heated for three is filtered. When mixed with v hours at one hundred (100) degrees C. this compression and who pulled. Vulcanized.

for one hour at one hundred and thirty five (135) degrees C. with ten per cent. of sulfur, it becomes solid and very elastic. To vulcanize it by means of protochlorid of sulfur, a solution of twenty (20) parts of' the sulfur dichlorid poppy oil alpha-naphthylamin product in one hundred and twenty (120) parts of toluene has added to it a solution of one part of protochlorid of sulfur in ten parts toluene. A thick mass immediately forms which, when dried on a water bath, becomes a brown product which.

is rather firm and elastic to compression but has little cohesion.

Example 9: A mixture of three parts of amido-azobenzol and eight'parts of xylene is heated to about one'hundred and fifteen (115) degrees C. so as to dissolve the major part of the amido-azobenzol, and then two parts of sulfur dichlorid oppy oil factice (Example 0) are then ad ed thereto. The mixture is next heated first for about ten hours at from one hundred and thirty to one hundred and thirty five (130 to 135) degrees C. and then for about six hours at from one hundred and thirty five to one hundred and forty (135 to 140) degrees C. The fused mass obtained is then largely diluted with toluene and afterward filteredobtained a brown black mass witha greenish luster, which is stringy in'a heated state and rather elastic and which is allowed. to dry in air. Its solution in toluene which is yellow brown, may be used as a yellow varnish.

Example 10: One (1) part of sulfur dichlo'rid castor oil factice (Example D) is mixed with five parts of anilin first heated for about six hours at from one hundred and thirty to one hundred and thirty five (130 to 135) degrees C. and then for about eight hours at from one hundred and thirty five to one hundred and forty (135 to 140) degrees C. The fused product is diluted with toluene and then filtered. By the addition of'alcohol to the filtrate a faintly colored mass is precipitated which is collected and washed with alcohol. In this state it is rather soluble in toluene, which solution may be used as acolorless varnish. When washed and dried at one hundred (100) degrees C. the product becomes rather hard and resinous. When hot however it is elastic. Example 11: A mixture of one (1) part of sulfur dichlorid cod liver oil factice (Example F), and four parts of anilin is heated I for about six-hours at from one hundred and thirtylto one hundred and thirty'five (130 to- 135) degrees C. The factice disappears little by little. The solution thus obtained is then diluted with about two volumes of benzol, then filtered and they filtrate precipitated with alcohol. The precipitate'which c'oagulates rapidly, is collected, washed with alcohol and then dissolved in benzol. A. limpid, faintly colored solution is thus obtained, which when applied to an object gives, after the solvent has been volatilized an adherent, colorless and easily handled film. By precipitating this solution with alcohol, a soft elastic light yellow brown .mass is deposited. Washed with alcohol and dried for one hour on a water bath it forms a mass which is elastic, solid and slightly sticky. Vulcanized for one hour at one hundfred and thirty (130) degrees C. with seven per cent. of sulfur, it becomes transformed into a very firm, but elastic, product.

; Example 12: A mixture of one part -of sulfur dichlorid boiled linseed oil factice (Example I) two parts of heavy benzin and three parts of anilin are caused to react together the mixture being'heated for about our hours at from one hundred and thirty to one hundred and thirty five (130 to 135) degrees C. The solution which is formed is diluted with twice its volume of benzol and then filtered. By the addition of alcohol to the filtrate a brown precipitate is deposited. The supernatant liquid is decantetd ofi'. Washed with alcohol and then dissolved in benzol, the residue yields a brownish solu- -tion which may be used as a varnish. Al-

cohol separates from this solution a soft elastic mass which, when driedon a Water bath,- is transformed into a brown, elastic and very solid mass.

Example 13:' A mixture of one part of linseed oil factice, (prepared with ten parts of linseed oil and three parts of protochlorid of sulfur) three parts of dimethylanilin and two parts of heavy benzin is slowly heated to about one hundred and thirty five(135) degrees C. and then the temperature .is gradually. raised to one hundred and forty (140) degrees C. and kept for five hours at from one hundred and forty to one hundred and fifty (14:0 to 150) degrees C. A mobile liquid is formed which is filtered after having been diluted with benzol. The filtrate has alcohol added to it which precipitates a semi-liquid brown substance, which when collected and Washed with alcohol, becomes viscous. Heated for two hours at one hundred and ten degrees C. it solidifies and forms a soft, brown and elastic product which, when vulcanized at one hundred and pulled.

Example 14: i llil ixture of one part of 'colza oil factice" (prepared with four parts of colza oil and one part of protochlorid of sulfur) and'three parts of dimethylanilin for about are heated for about-two hours at from one hundred and thirty to one hundred and thirty five $180 to '135) degrees C. and then ve hours at from one hundred and forty to one hundred and fifty (1&0 to 150) degreesG. The fused mass is poured into benzol, filtered and the filtrate then precipitated with alcohol. A brown liquid mass is deposited' Collected and washed with alcohol it forms a viscous substance which polymerizes by being heated for'about tWo hours at from onehundred and'twenty five to one hundred and thirty (125 to 130) degrees C. and then forms a dark brown transparent rather soft and sticky product which is elastic to compression.

Mixed with ten per cent. of sulfur and vulcanized for one hour at one hundred andthirty five (135) degrees C. this mass turns into a black substance still slightly soft and elastic.

Other products derived from factices and amins are indicated in the following table:

Tem eratures Properties of the Autoclave...'.

Elastic, rather solid, light b r o w n,

ssh htly sticky.

Elastic, solid brow-n.

Linseed oil (Ex. A 1 Meta-amidopheno? 5 B3 33? C Imperiectly solu- Xylene 15 ble in xylene.

China wood oil (Ex. B) 1 Rather elastic, rather per cent, monomethyl- 18 125-130 C. firm, s l i g h t l y amin. 20 hours. sticky, b r o w n. Autoclave Partially soluble in xylene.

China wood oil (Ex.' B) L 1 Rather hard. Insolu- Water 10 3011mm utoclave P py oil (Ex. 6) 1 i o Elastic to compres- M za t atoluylenediamin 1 ifi gg sion, medium cohe- Xylene 4 son, brown. Partially soluble in benzol.

Popp oil (Ex. 0). 1 Rather elastic cohe- Benzidin 3 1 51? 0 sion good, brown. Toluene 10 Partially soluble in xylene.

uble in xylene.

'lem eratures Initial meteriela-Factice Properties of the ofgg fi ggs masses obtained.

on 11(E E) i in r fir b V9 0 X. n as 10 m lOWn. Meta-amldobenzoic we" 2 sli hu soluble in Xylene. 8 toluene.

Olive 01103113 1 Elastic soft,slightl Acetoparaxylidin.... 2 gaiga f sticky,brown. Ini Xylene 7 perfectly soluble in toluene.

.oigdized linseed oil (Ex. 3 0 new eogiesion 0o rown.

Ani in 1o 15 f n hu soluble in toluene Rather elastic, firm,

Sulfureted castor oil (Ex. 1 Q o H P330439 lightbrown. Solu- Rather *elastic, solid Oxidized and sulfureted 1 linseed oil rotochlorid l-l45 C. dark brown. Parof sulfur (3i 0 hours tially soluble in Dimethylanilin 6 benzol.

Linseed protobromid of 1 Elastic, rather soft,

1 Slfllllif 1). 25 20 C slightly sticllrymlmtime amin er er ec so u e in cent. y p 1511mm Eenzoh Autoclave Linseed tetrachlorid of 1 0 Rather elastic yelsuliur low of slightly resi- Ani1m..... 4 nous appearance.

. Soluble in xylene.

Linseed suhiodid of 5111- 1 e 0 Rather elastic soft, fur 2 9 2 5 5 brown. Ini p er- Peraxylidm 5 fectly soluble in xylene.

Below are given the factices enumerated 30) in the above six sections of the table.

(1) Factice obtained by the action of fifteen (15) parts of sulfur protochlorid upon onehundred (100) parts of oxidized linseed oil, this latter being previously diluted with 35 one hundred (100) parts of benzol. For the preparation of the oxidized linseed oil see Example G..

(2) Factice obtainedby causing twelve (12) parts of protochlorid of sulfur to react 4o upon one hundred (100) parts of castor oil, previously sulfureted with four (4) parts of sulfur at a temperature of one hundred to two hundred (100 to 200). C.

(3) Factice prepared by the action of twelve (12) parts of protochlorid of sulfur upon one hundred (100) parts of oxidized and sulfureted linseed oil (see Example I for its preparation) thisoil being previously diluted with fifty parts of benzol. 50

( l) Factice obtained by the reaction of stances which consists in subjecting a factice fifty five (55) parts of protobromid of sulfur with one hundred (100) parts of linseed oil.

(5) Factice obtained-by causing one (1) part of tetrachlorid of sulfur freshly prepared and kept at a low temperature minus twenty two degrees (22-) C.'to act upon four (4:) parts of linseed oil cooled down to minus fifteen degrees (15) C. The temperature is then allowed to rise slowly to ordinary temperature.

(6) Factice prepared by the actionv of a mixture of four (4:) parts of sub-iodid of sulfur and ten (10) parts of benzol upon five" (5) parts of linseed oil.

What I claim is 1. The process of making rubber-like substances which consists in subjecting a factice to the action of an amin, substantially asand for the purpose set forth. v

2. The process of making rubber-like subto the action of an amin, in the presence of a substance which facilitates the reaction, substantially as described.

3. The process of making rubber-like substances which consists in subjecting a factice 'to the action of an amin and then hardening the substance thus produced, substantially as described. 4

4:. The process of making rubber-like substances which consists in subjecting a factice to the action of an amin, in the presence of a substance which facilitates the reaction, and then hardening the substance thus produced, substantially as described.

5'. The process of making rubber-like substances which consists in subjecting a factice to the action of an amin, hardening the substance thus produced, and subsequently vulcanizing with sulfur, substantially as described.

6. The process of making rubber-like substances which consists in subjecting a factice to the action of an amin, in the presence of a substance which facilitates the reaction, hardening the substance thus produced, and subsequently vulcanizing with sulfur, substantially as described.

Signed at American consulate general, Marseilles, France, this fourteenth day of December, 1911.

GEORGES NUTH- Witnesses:

GANUG, E. BARATIER. 

